Biogenic methane production enhancement systems

ABSTRACT

Systems for enhanced in-situ or perhaps even ex-situ biogenic methane production from hydrocarbon-bearing formations ( 1 ) including coal seam, oil shale, coal, coal derivates and the like are presented in embodiments such as but not limited to: increasing and perhaps even selection of microbial populations ( 2 ), amending CBM water and other microbe-containing media, diminishing sulfate reduction competition, enhancing organic matter concentrations and generation of biogenic methane ( 10 ), universally treating hydrocarbon-bearing formations, and introducing amendments ( 3 ) to hydrocarbon-bearing formations.

This application is the United States National Stage of internationalapplication no. PCT/2006/031723 filed 14 Aug. 2006 which claims thebenefit of U.S. Provisional Application No. 60/707,697 filed Aug. 12,2005, each hereby incorporated by reference herein. Any priority case ishereby incorporated by reference herein.

ACKNOWLEDGMENT OF GOVERNMENT SUPPORT

This technology relates to work performed under U.S. DOE CooperativeAgreement #DE-FC26-98FT40322. The U.S. government may have certainrights in this inventive technology, including “march-in” rights, asprovided for by the terms of U.S. DOE Cooperative Agreement#DE-FC26-98FT40322.

TECHNICAL FIELD

The present invention relates to biogenic production of methane inex-situ and even in-situ systems. Specifically, embodiments may providevarious kinds of amendments such as but not limited to microbialpopulation stimulation amendments, indiscriminate microbial populationstimulation amendments, additional microbial population stimulationamendments, sulfate reduction competition shield amendments,predetermined microbial population stimulation amendments, and the likewhich can be introduced into various hydrocarbon-bearing formations toenhance the production of biogenic methane.

BACKGROUND OF THE INVENTION

Methane may be mainly formed through thermogenic and methanogenic(biogenic) processes. Biogenic methane may be believed to consist ofabout 20-40% of the total methane storage on earth, and higher ratios(such as about 65%) under favorable bio-geological conditions.Methanogens may be strictly anaerobic archaebacteria. Biogenic methaneproduction may be carried out by methanogens through methanogenesis, inwhich carbon dioxide and small organic molecules may be converted tomethane through a series of biological reactions perhaps by microbialpopulations as those skilled in the art can appreciate. Isotopefractionation studies may have verified that biogenic methane isactively produced in coal seam and oil shale and the like, which maycontain a rich source of small organic compounds to serve as substratesfor methanogenesis. Accordingly, methanogenesis can produce methane fromoil shale, coal, coal derivatives, lignite, and the like by removinghydrogen and carbon from a source.

Methane production processes may be a versatile biotechnology capable ofconverting almost all types of polymeric materials to methane and carbondioxide under anaerobic conditions. This may be achieved as a result ofthe consecutive biochemical breakdown of polymers to methane and carbondioxide in an environment in which a variety of microorganisms which mayinclude fermentative microbes (acidogens); hydrogen-producing,acetate-forming microbes (acetogens); and methane-producing microbes(methanogens) harmoniously grow and produce reduced end-products.Anaerobes may play important roles in establishing a stable environmentat various stages of methane production.

Coal bed methane (“CBM”), as an example, may demonstrate that CBM wateroverlaying coal seam may be able to support observable methaneproduction under anaerobic conditions. Methane production may not havebeen observed in sterile controls, possibly confirming it may be amicrobially mediated process. Indigenous methanogens have been detectedas present in the coal cores extracted from the Powder River Basin(PRB), indicating a potential of enhancing the methanogenic activitiesas an economically feasible approach to harvest bioreservoir of CBM.

Currently, an effective technology to identify and enhance biogenicmethane production in coal seam, oil shale, and the like may be lacking.For example, U.S. Pat. No. 6,543,535 to Converse, hereby incorporated byreference, includes analysis of subterranean formations and stimulatingactivity of microbial consortia based on the analysis in a subterraneanformation to convert hydrocarbons to methane. However, applicability ofenhancement of biogenic methane production to a wide variety ofsituations and even efficient enhancement of biogenic methane is desiredin the industry.

DISCLOSURE OF THE INVENTION

It is therefore an object of the present invention, in embodiments, toprovide an identification of potential methane production sources.

It is yet another object of the present invention, in embodiments, toenhance biogenic methane production from coal seam, oil shale, coal,coal derivatives, lignite, and the like.

It is object of the present invention, in embodiments, to introduceamendments to hydrocarbon-bearing formations perhaps even as in apre-treatment step to biogenic methane production.

It is yet another object of the present invention, in embodiments, foruniversal treatment such as with introduction of predeterminedamendments to hydrocarbon-bearing formations perhaps even as in apre-treatment step to biogenic methane production.

It is another object of the present invention, in embodiments, tomanipulate parameters that affect the occurrence and rates ofmethanogenesis in coal seam, oil shale, and the like.

It is yet another object of the present invention, in embodiments, todiminish sulfate reduction competition.

It is another object of the present invention, in embodiments, to starveand perhaps even select capable microbial populations such asmethanogens.

It is another object of the present invention, in embodiments, toenhance organic matter release from sources such as coal, coal seam, oilshale and the like.

It is another object of the present invention, in embodiments, toprovide ex situ systems and in-situ systems for biological methaneproduction.

It is yet another object of the present invention, in embodiments, tobeneficially use recycled water such as coal bed methane water andagriculture wastes containing organic constituents, and the like formethane production.

It is yet another object of the present invention, in embodiments, todegrade hydrocarbon and other organic components during or perhaps evenafter the operations of exploring and extracting oil shale, coal,lignite and the like. The components, for example, may be residual oilremained in oil shale or produced water, residual organic compounds incoal or produced water.

Naturally, further objects, goals and embodiments of the inventions aredisclosed throughout other areas of the specification.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an example of data from treatments on oil shale and thepercentage of increase in methane in accordance with some embodiments ofthe present invention.

FIG. 2 shows an example of data from treatments on oil shale and thepercentage of increase in methane in accordance with some embodiments ofthe present invention.

FIG. 3 shows an example of data for cumulative methane production frommicrobes with coal and CBM co-produced water in accordance with someembodiments of the present invention.

FIG. 4 shows an example of data for cumulative methane production frommicrobes with coal and groundwater in accordance with some embodimentsof the present invention.

FIG. 5 shows an example of data for cumulative methane production frommicrobes with lignite and CBM co-produced water in accordance with someembodiments of the present invention.

FIG. 6 shows an example of data for cumulative methane production frommicrobes with lignite and groundwater in accordance with someembodiments of the present invention.

FIG. 7 shows an example of data for cumulative methane production frommicrobes with diesel-contaminated soil and CBM co-produced water inaccordance with some embodiments of the present invention.

FIG. 8 shows an example of data for cumulative methane production frommicrobes with diesel-contaminated soil and groundwater in accordancewith some embodiments of the present invention.

FIG. 9 shows an example of data for cumulative methane production frommicrobes with peat and CBM co-produced water in accordance with someembodiments of the present invention.

FIG. 10 shows an example of data for cumulative methane production frommicrobes with peat and groundwater in accordance with some embodimentsof the present invention.

FIG. 11 shows an example of data for cumulative methane production frommicrobes with oil shale and groundwater in accordance with someembodiments of the present invention.

FIG. 12A shows an example of data for cumulative carbon dioxideproduction from gas produced in microbes with oil shale and groundwaterin accordance with some embodiments of the present invention.

FIG. 12B shows an example of data for methane to carbon dioxide ratiosfrom gas produced in microbes with oil shale and groundwater inaccordance with some embodiments of the present invention.

FIGS. 13A and 13B show an example of data for cumulative methaneproduction from microbes with oil shale and groundwater which wereincubated at 30° C. after 180 days in accordance with some embodimentsof the present invention.

FIG. 14A shows an example of data for cumulative carbon dioxideproduction from gas produced in microbes with oil shale and groundwaterwhich were incubated at 30° C. after 180 days in accordance with someembodiments of the present invention.

FIG. 14B shows an example of data for methane to carbon dioxide ratiosfrom gas produced in microbes with oil shale and groundwater which wereincubated at 30° C. after 180 days in accordance with some embodimentsof the present invention.

FIG. 15A shows an example of data for methane production from oil shalecores (fractured and unfractured) with various enhancements inaccordance with some embodiments of the present invention.

FIG. 15B shows an example of data for carbon dioxide production from oilshale cores (fractured and unfractured) with various enhancements inaccordance with some embodiments of the present invention.

FIG. 16 represents an ex-situ environment for biogenic methaneproduction in accordance with some embodiments of the present invention.

FIG. 17A-17F represents a hydrocarbon-bearing formation of whichamendments may be carried to an oil shale layer to enhance biogenicmethane production in accordance with some embodiments of the presentinvention.

FIG. 18 is a conceptual representation of an introduction of varioustypes of amendments to any kind of hydrocarbon-bearing formation inaccordance with some embodiments of the present invention.

MODE(S) FOR CARRYING OUT THE INVENTION

The present invention includes a variety of aspects, which may becombined in different ways. The following descriptions are provided tolist elements and describe some of the embodiments of the presentinvention. These elements are listed with initial embodiments, howeverit should be understood that they may be combined in any manner and inany number to create additional embodiments. The variously describedexamples and preferred embodiments should not be construed to limit thepresent invention to only the explicitly described systems, techniques,and applications. Further, this description should be understood tosupport and encompass descriptions and claims of all the variousembodiments, systems, techniques, methods, devices, and applicationswith any number of the disclosed elements, with each element alone, andalso with any and all various permutations and combinations of allelements in this or any subsequent application.

This present invention includes several embodiments in in-situ andex-situ enhancing of biogenic methane production from coal seam, oilshale, coal, waste coal, coal derivatives, peat, lignite, oilformations, petroleum sludge, drill cuttings, tar sands,hydrocarbon-contaminated soil, and the like. In embodiments, the presentinvention may include an evaluation of biogenic methane reserve in coalseam, oil shale and the like with ex-situ or perhaps even in-situenvironments. It may be desirable to provide a two component system toestimate and predict the potential of biogenic methane production:methanogenic population and perhaps substrate bioavailability.Indigenous core samples may be collected from the sites of interest.Core samples may be crushed and extracted properly. Microbial samplepreparation and real time Polymerase Chain Reaction (“PCR”) may be usedto determine the population density of methanogens. Total dissolvedorganic carbon (“DOC”) can be quantified from the core samples. Astoichiometric calculation can be used to predict the amount of methanethat can be released from the site. As a non-limiting example, table 1,below, represents a conversion from carbon to methane. Specifically,Table 1 is based on 64 mol of C converted to 49 mol of methane.

TABLE 1 g CH4/kg lbs. CH4/ton Carbon Source mg C/kg mol C/kg mol CH4/kgsource Source Source Oil 3865 0.322083 0.246595052 2.9591406256.523721422 Shale Coal 22.092 0.001841 0.001409516 0.0169141880.037289018 Lignite 506.94 0.042245 0.032343828 0.388125938 0.855662442

In embodiments, the present invention may provide methods forenhancement of biogenic methane production and even biogenic methaneproduction systems. It may be desirable to provide a population boost ofindigenous methanogens. In some embodiments, the present invention mayprovide a hydrocarbon-bearing formation perhaps initially having amicrobial population perhaps even at least one, at least two or evenmore microbial populations. Microbial populations may be an indigenousmicrobial population in that they may have originated or may even occurnaturally in an area or environment. For example, a microbial populationmay have pre-existed with a hydrocarbon-bearing formation. Of course, inother embodiments, a microbial population may be added to ahydrocarbon-bearing formation to enhance methanogenic activities.

In the various embodiments discussed herein, a hydrocarbon-bearingformation or even a hydrocarbon-bearing formation environment mayinclude, but is not limited to, oil shale, coal, coal seam, waste coal,coal derivatives, lignite, peat, oil formations, tar sands,hydrocarbon-contaminated soil, petroleum sludge, drill cuttings, and thelike and may even include those conditions or even surroundings inaddition to oil shale, coal, coal seam, waste coal, coal derivatives,lignite, peat, oil formations, tar sands, hydrocarbon-contaminated soil,petroleum sludge, drill cuttings, and the like. In some embodiments, thepresent invention may provide an in-situ hydrocarbon-bearing formationsometimes referred as an in-situ hydrocarbon-bearing formationenvironment or in-situ methane production environment. Embodiments mayinclude an ex-situ hydrocarbon-bearing formation sometimes referred toas an ex-situ hydrocarbon-bearing formation environment or an ex-situmethane production environment. In-situ may refer to a formation orenvironment of which hydrocarbon-bearing sources may be in theiroriginal source locations, for example, in-situ environments may includea subterranean formation. Ex-situ may refer to formations orenvironments where a hydrocarbon-bearing formation has been removed fromits original location and may perhaps even exist in a bioreactor,ex-situ reactor, pit, above ground structures, and the like situations.As a non-limiting example, a bioreactor may refer to any device orsystem that supports a biologically active environment.

The present invention may provide, in embodiments, starvation andperhaps even selection of capable methanogens. Upon the populationgrowth of methanogens, initially amended substrates can be depletedwithin a short period of time. Methanogens can go through a “starvation”period in which an “easy food source” may no longer be available. Arapid adaptation, genetic mutation, and perhaps even gene transferthrough plasmids, transposons and other possible pathways may perhapsselectively enhance the methanogens that can utilize small organiccompounds from coal seam, oil shale, and the like. These small organiccompounds may preexist or perhaps even originate from the degradation oforganic matter in the coal, oil shale, or the like. This may provide anenhanced methane production and may even provide biogenically generatedmethane derived from a sustained boosted microbial population.

At least one indiscriminate microbial population stimulation amendmentmay be introduced or perhaps even delivered into a hydrocarbon-bearingformation. Microbial populations may microbially consume at least oneindiscriminate microbial population stimulation amendment. As a resultof the microbial consumption of at least one indiscriminate microbialpopulation stimulation amendment, a blanket boosting of the microbialpopulations may occur and may provide at least some boosted microbialpopulations. This may provide an increase of perhaps all of themicrobial populations. As the microbes consume the amendments, microbialdepletion of at least one indiscriminate microbial populationstimulation amendment may result. Accordingly, at least one of theboosted microbial populations may begin to starve and thus providing atleast one starved microbial population. Only those microbial populationswhich can survive on the remaining amendments, organic matter created,and perhaps even the hydrocarbon-bearing formation amendments maysurvive. As a result, a selective reduction of any starved, boostedmicrobial population(s) may occur. Conversely, embodiments may providefor selectively sustained at least one sustained, boosted microbialpopulation. Boosted microbial population(s) may then be stimulated tomicrobially convert hydrocarbons to methane.

As discussed in the various embodiments herein, stimulating at least onemicrobial population with at least one amendment may include increasingorganic matter concentrations within a formation or environment andperhaps even feeding at least one microbial population. An introductionof amendments or the like can cause stimulation of microbial populationsperhaps to even create a series of metabolic interactions amongmicrobial populations. Introduction of amendments may be referred to aspretreatment in some embodiments. As a result, biogenically generatedmethane may be derived from a series of metabolic interactions among atleast one microbial population.

In embodiments, at least one of the microbial populations may include amethanogen population and accordingly, such selective processes maytherefore increase an indigenous methanogenic population. Methanogensmay be a main player in methane production. It may be that a higher apopulation of methanogens may result in a larger production of methane.In embodiments, an indiscriminate microbial population stimulationamendment may include simple or perhaps even easy substrates, such asbut not limited to dairy wastes and the like, and may be used to feed awhole microbial community perhaps as a pretreatment step. This may boostup populations in the microbial community such as but not limited tomethanogens, the associated bacterial species, for example, fermenters,and the like microbial community populations.

Readily available substrates such as corn syrup, emulsified oil,lactate, fresh or spoiled milk, any combination thereof, and the likemay be used as, but is not limited to, an indiscriminate microbialpopulation stimulation amendment which may even be introduced into ahydrocarbon-bearing formation. In other embodiments, an introduction ofindiscriminate microbial population stimulation amendments can becombined with a fracturing process as discussed below. Indiscriminatemicrobial population stimulation amendments may have no selectiveness tomicrobes. As such, a blanket boost of microbial populations may beexpected. Injected substrates can be depleted within short period oftime, as they may be preferred by every microbial group. Upon thedepletion of the injected substrates, microbes may be exposed to aselection. It may be desirable to discontinue any introduction of anyindiscriminate microbial population stimulation amendment to ahydrocarbon-bearing formation so that those injected amendments can bedepleted. Only those capable of degrading a hydrocarbon-bearingformation may sustain their metabolism and growth. Other species couldbe outcompeted due to starvation of at least one of the boostedmicrobial populations. The end result may provide a chain of microbialpathways. This pathway can degrade a hydrocarbon-bearing formationthrough intermediates and eventually produce methane. The initialaddition of an indiscriminate microbial population stimulationamendment(s) may increase microbial population, therefore generatingmethane from at least one boosted microbial population and may providemethane produced from microbial conversion of hydrocarbons.

In other embodiments, at least one additional microbial populationstimulation amendment may be introduced into a hydrocarbon-bearingformation environment. Such introduced additional microbial populationstimulation amendment may be used to further increase methane productionby microbial population stimulation. An introduced additional microbialpopulation stimulation amendment may include, but is not limited to,nitrogen, phosphorous, vitamins, organic carbon, biotin, folic acid,pyrodoxine hydrochloride, thiamine hydrochloride, riboflavin, nicotinicacid, DL-calcium panthenate, vitamin B12, p-aminobenzoic acid, lipoicacid, any combination thereof, and the like. In another embodiment, anintroduced additional microbial population stimulation amendment mayalso include, but is not limited to, biowastes, lactate, milk, returnedmilk, nitrogen, phosphorous, vitamins, salts, micronutrients,surfactants, acids, bases, oxidants, acetic acid, sodium hydroxide,percarbonate, peroxide, sodium carbonate, sodium bicarbonate, hydratedsodium carbonate, any combination thereof and the like.

The present invention may provide in embodiments, a beneficial use ofrecycled water such as, but not limited to, produced water, groundwater,local groundwater, water from coal bed methane (“CBM”), wastewater, coalproduced water, CBM produced water, and any reused water or perhaps evenreused liquid. One design of this technology may use recycled water as acarrier to enhance biogenic methane production. It may offer abeneficial use of the water and an innovative method of its disposal.For example, in the CBM case, produced water from a CBM site can bebeneficially used as a carrier. Amendments such as substrates(biowastes, lactate, milk, etc.) and perhaps even essential nutrients(nitrogen, phosphorus, vitamins, salts, and other micro nutrients, etc.)can be amended to recycled water. Recycled water carrying an amendmentor amendments (the various types of amendments which can be injected arediscussed herein) may be injected into a hydrocarbon-bearing formation.Recycled water may even be injected into ex-situ or even in-situ methaneproduction environments. In some embodiments, recycled water may havemicrobial populations, methanogen populations, or the like existing inthe water from a previous treatment. These residing microbes,methanogens or the like may be delivered to a hydrocarbon-bearingformation and may even further enhance biogenic methane production.

For example, an amended produced water may be injected back into thecoal seam as those skilled in the art can appreciate. An injectionelement such as recycled injection amendment, a produced water injectionelement, a groundwater injection element, or perhaps even a coal bedmethane water injection element, and the like may include those elementswhich allow the addition of an amended water in a hydrocarbon-bearingformation perhaps under pressure, by gravity forces, other waterinjection methods and elements, and the like as those skilled in the artcan appreciate. An amended produced water may assist in exponentialgrowth of a population of methanogens. As a result of the methanogenicactivities during this phase, biogenic methane may be generated, andperhaps even amended substrates can serve as a main electron source.Also during this process, other non-methanogenic populations can beincreased due to favorable conditions provided by the amendments. Forexample, some microbial groups may be important in degrading coal seams,coal, coal derivatives, oil shale, and the like and may release smallorganic compounds that can be amenable to methanogens to produce methanein later stages.

In yet other embodiments, the present invention may provide diminishingsulfate reduction competition in a methane production environment.Sulfate may be a competing process to methanogenesis and sulfide, aproduct of sulfate reduction, may be toxic to microbial populations suchas methanogens. In embodiments, it may be desirable to introduce asulfate reduction competition shield amendment into ahydrocarbon-bearing formation. A sulfate reduction competition shieldamendment may include, but is not limited to, nitrite, ferrous iron, acombination of the two, and the like and may even be delivered to ahydrocarbon-bearing formation environment to perhaps reduce or eveneliminate sulfate reduction competition and its products. If a highsulfate concentration may be present in the coal seam, oil shale, coal,coal derivatives, and the like, injected water, injected recycled water,or the like, trace amounts of nitrite and perhaps even a stoichiometricamount of ferrous iron can be introduced as amendments. Nitrite may bean effective inhibitor to sulfate reduction and ferrous iron can bindwith sulfide. These “double” shields can eliminate the adversecompetition from sulfate reduction and ensure a population growth andactivities of methanogens.

In other embodiments, the present invention may include an induction orperhaps even enhancement of organic matter released from coal, oil shaleand the like. Physical (e.g., fracture and the like) and chemicalapproaches (e.g., treating with surfactants, acids, bases, oxidants,such as but not limited to acetic acid, sodium hydroxide, percarbonate,peroxide and the like) can be applied to enhance an availability oforganic matters in coal and oil shale. These methods may be used tobreak down coal, oil shale, lignite, coal derivatives and the likestructures to release more organic matters, or perhaps even to make themmore vulnerable to be degraded into smaller organic compounds. Theseorganic matters may be consumed by methanogens to create methane.

The present invention may include, in embodiments, methods of ex-situenhancing biogenic methane production and perhaps even ex-situ biogenicmethane production systems. A hydrocarbon-bearing formation (1) may beextracted from a subterranean source (16) as may be represented in FIG.17B. At least one microbial population (2)—which may include, inembodiments, at least one methanogen population—may be extracted with ahydrocarbon-bearing formation and both may be placed in an ex-situmethane production environment (17). In embodiments and as one exampleis shown in FIG. 16, an ex-situ methane production environment mayinclude a bioreactor as discussed herein. Introduction of at least onemicrobial population stimulation amendment to an ex-situ methaneproduction environment (15) may be desired. Such introduced microbialpopulation stimulation amendment may include amendments such as but notlimited to, biowastes, lactate, milk, returned milk, nitrogen,phosphorous, vitamins, salts, micronutrients, surfactants, acids, bases,oxidants, acetic acid, sodium hydroxide, percarbonate, peroxide, sodiumcarbonate, sodium bicarbonate, hydrated sodium carbonate, anycombination thereof, and the like. Amendments may provide stimulation ofa microbial population(s) as discussed above. Accordingly, biogenicallygenerated methane (32) may be produced in an ex-situ methane productionenvironment as derived from the introduced microbial populationstimulation amendment, in various embodiments.

FIG. 18 is a conceptual representation of a hydrocarbon-bearingformation (1) having at least one microbial population (2). Inembodiments, a hydrocarbon-bearing formation (1) may be present in anin-situ methane production environment or perhaps even an ex-situmethane production environment. Addition of various types of amendments(3), as herein discussed, may be added to the hydrocarbon-bearingformation (1). Various biogenic processes (24), as herein discussed, mayoccur and biogenically generated methane (10) may result.

As discussed herein, various embodiments of the present invention mayinclude generating methane from a stimulated microbial population.Accordingly, methane may be generated by microbial conversion ofhydrocarbons. Methane can be collected with a methane collection element(11) for further processing. Such methane collection may be obtained byconventional methods as those skilled in the art can appreciate. Forexample, pressure methods may be used or perhaps even head-spacecollection methods, and the like can be used for methane collection.

As may be understood in FIG. 16, generally a hydrocarbon-bearingformation (31) may be placed in an ex-situ methane productionenvironment (15). Amendments—a variety of which are discussed herein—maybe added to the hydrocarbon-bearing formation through an amendmentinjection element (22). A sampling port (30) may be included, inembodiments. Biogenically generated methane (32) may be produced and maybe collected with a methane collection element (11).

The present invention may provide, in embodiments, methods for universalenhancement of biogenic methane production and even universal biogenicmethane production systems. It may be desirable to apply a universaltreatment to a hydrocarbon-bearing formation of which the user does notneed to do any specific analysis of the formation—perhaps even theexclusion of any analysis of existing microbial populations in thehydrocarbon-bearing formation. This universal treatment may provide apredetermined recipe to apply to a hydrocarbon-bearing formation toallow efficient enhancement of methane production. Such predeterminationmay include table look up, analysis from pretreatments, laboratory basedanalysis, and the like.

A hydrocarbon-bearing formation environment perhaps even having at leastone microbial population may be provided. In embodiments, the presentinvention may include an indigenous microbial population which may havepre-existed with a hydrocarbon-bearing formation as further discussedherein. Of course, a hydrocarbon-bearing formation environment may be inan in-situ or perhaps even in an ex-situ environment. At least onepredetermined microbial population stimulation amendment may beintroduced to a hydrocarbon-bearing formation. For example, a generalrecipe may be used to convert methane in the subsurface for differentmaterials. These materials may include but are not limited to coal, oilshale, lignite, and the like. An introduced predetermined microbialpopulation stimulation amendment may include but is not limited to, acoal specific predetermined amendment, an oil shale specificpredetermined amendment, a lignite specific predetermined amendment, acoal seam specific predetermined amendment, a waste coal specificpredetermined amendment, a coal derivative specific predeterminedamendment, a peat specific predetermined amendment, an oil formationspecific predetermined amendment, a tar sand specific predeterminedamendment, a petroleum sludge specific predetermined amendment, a drillcutting specific predetermined amendment, a hydrocarbon-contaminatedsoil specific predetermined amendment, and the like. Introduction ofpredetermined microbial population stimulation amendment(s) may occurthrough injection into a hydrocarbon-bearing formation as hereindiscussed. The amendments may therefore provide stimulation of themicrobial population(s)—such microbial population(s) may include atleast one methanogen population, in embodiments—thus generating methanefrom the stimulated microbial population(s). Again, the methane may becollected as discussed herein.

Generally, a predetermined microbial population stimulation amendmentmay include ingredients, such as but not limited to, nitrogen,phosphorous, vitamins, organic carbon, biotin, folic acid, pyrodoxinehydrochloride, thiamine hydrochloride, riboflavin, nicotinic acid,DL-calcium panthenate, vitamin B12, p-aminobenzoic acid, liponic acid,any combination thereof, and the like.

Of course other amendments may be introduced, such as but not limitedto, biowastes, lactate, milk, returned milk, nitrogen, phosphorous,vitamins, salts, micronutrients, surfactants, acids, bases, oxidants,acetic acid, sodium hydroxide, percarbonate, peroxide, sodium carbonate,sodium bicarbonate, hydrated sodium carbonate, any combination thereof,and the like. These amendments may further enhance biogenic methaneproduction.

In embodiments, it may be desirable to apply a pretreatment to thehydrocarbon-bearing formation, perhaps even to a coal formation, beforeany addition of predetermined microbial population stimulationamendment(s). This may include the addition of a basic solution to bringthe pH to 10. It may be desirable to wait for 24-48 hours and adjust pHdown to less than 8 thereafter, in embodiments. The pH may be measuredin the overlaying water. In other embodiments, it may be desirable toapply a pretreatment to the hydrocarbon-bearing formation, perhaps evenan oil shale formation, before any addition of predetermined microbialpopulation stimulation amendment(s). This may include the addition of abasic solution to lignite to bring pH to 10. It may be desirable to waitfor 24-48 hours and adjust pH down to 9 thereafter, in embodiments. Inyet other embodiments, instead of basic solution, commercial surfactantscan be used for pre-treatment.

The following lists non-limiting examples of various predeterminedamendments which can be combined or applied separately and may even beused with in-situ environments. In some instances, a range of +/−30% maybe added to the amounts in the following formulas. These are examplesonly and other predetermined amendments may be used with the varioushydrocarbon-bearing formations for enhancement of biogenic methaneproduction.

One example of a coal specific predetermined amendment may include:

-   -   Add 220 g of N per kg of coal (NOTE: calculate the amount of        fertilizer based on its N content)    -   Add 50 g P per kg of coal (NOTE: calculate the amount of        fertilizer based on its P content)    -   Add vitamins in the following amounts per kg coal        -   0.333 g Biotin        -   0.333 g Folic Acid        -   1.667 g Pyrodoxine Hydrochloride        -   0.833 g Thiamine Hydrochloride        -   0.833 g Riboflavin        -   0.833 g Nicotinic Acid        -   0.833 g DL-Calcium Panthenate        -   0.017 g Vitamin B₁₂        -   0.833 g p-Aminobenzoic Acid        -   0.833 g Lipoic Acid

Another example of a coal specific predetermined amendment may include:

-   -   Add 625 g of organic C per kg coal to increase methanogen        population (NOTE: calculate the amount of organic C source based        on its organic C content)    -   Add 440 g of N per kg of coal (NOTE: calculate the amount of        fertilizer based on its N content)    -   Add 97 g P per kg of coal (NOTE: calculate the amount of        fertilizer based on its P content)    -   Add vitamins in the following amounts per kg coal        -   0.333 g Biotin        -   0.333 g Folic Acid        -   1.667 g Pyrodoxine Hydrochloride        -   0.833 g Thiamine Hydrochloride        -   0.833 g Riboflavin        -   0.833 g Nicotinic Acid        -   0.833 g DL-Calcium Panthenate        -   0.017 g Vitamin B₁₂        -   0.833 g p-Aminobenzoic Acid        -   0.833 g Lipoic Acid

One example of an oil shale specific predetermined amendment mayinclude:

-   -   Add 17.5 to 70.0 g of N per kg of oil shale (NOTE: calculate the        amount of fertilizer based on its N content)    -   Add 4.0 to 15.5 g P per kg of oil shale (NOTE: calculate the        amount of fertilizer based on its P content)    -   Add vitamins in the following amounts per kg oil shale        -   0.333 g Biotin        -   0.333 g Folic Acid        -   1.667 g Pyrodoxine Hydrochloride        -   0.833 g Thiamine Hydrochloride        -   0.833 g Riboflavin        -   0.833 g Nicotinic Acid        -   0.833 g DL-Calcium Panthenate        -   0.017 g Vitamin B₁₂        -   0.833 g p-Aminobenzoic Acid        -   0.833 g Lipoic Acid

Another example of an oil shale specific predetermined amendment mayinclude:

-   -   Add 50 to 200 g of organic C per kg oil shale to increase        methanogen population (NOTE: calculate the amount of organic C        source based on its organic C content)    -   Add 35 to 140 g of N per kg of oil shale (NOTE: calculate the        amount of fertilizer based on its N content)    -   Add 7.75 to 31.00 g P per kg of oil shale (NOTE: calculate the        amount of fertilizer based on its P content)    -   Add vitamins in the following amounts per kg oil shale        -   0.333 g Biotin        -   0.333 g Folic Acid        -   1.667 g Pyrodoxine Hydrochloride        -   0.833 g Thiamine Hydrochloride        -   0.833 g Riboflavin        -   0.833 g Nicotinic Acid        -   0.833 g DL-Calcium Panthenate        -   0.017 g Vitamin B₁₂        -   0.833 g p-Aminobenzoic Acid        -   0.833 g Lipoic Acid

One example of a lignite specific predetermined amendment may include:

-   -   Add 170 g of N per kg of lignite (NOTE: calculate the amount of        fertilizer based on its N content)    -   Add 37 g P per kg of lignite (NOTE: calculate the amount of        fertilizer based on its P content)    -   Add vitamins in the following amounts per kg lignite        -   0.333 g Biotin        -   0.333 g Folic Acid        -   1.667 g Pyrodoxine Hydrochloride        -   0.833 g Thiamine Hydrochloride        -   0.833 g Riboflavin        -   0.833 g Nicotinic Acid        -   0.833 g DL-Calcium Panthenate        -   0.017 g Vitamin B₁₂        -   0.833 g p-Aminobenzoic Acid        -   0.833 g Lipoic Acid

Another example of a lignite specific predetermined amendment mayinclude:

-   -   Add 478 g of organic C per kg lignite to increase methanogen        population (NOTE: calculate the amount of organic C source based        on its organic C content)    -   Add 335 g of N per kg of lignite (NOTE: calculate the amount of        fertilizer based on its N content)    -   Add 75 g P per kg of lignite (NOTE: calculate the amount of        fertilizer based on its P content)    -   Add vitamins in the following amounts per kg lignite        -   0.333 g Biotin        -   0.333 g Folic Acid        -   1.667 g Pyrodoxine Hydrochloride        -   0.833 g Thiamine Hydrochloride        -   0.833 g Riboflavin        -   0.833 g Nicotinic Acid        -   0.833 g DL-Calcium Panthenate        -   0.017 g Vitamin B₁₂        -   0.833 g p-Aminobenzoic Acid        -   0.833 g Lipoic Acid

Non-limiting examples of ex-situ applications which may be applicable tothose hydrocarbon-bearing formations such as but not limited to coal,oil shale, lignite, peat, hydrocarbon-contaminated soil, petroleumsludge, waste coal, and the like may include:

-   -   1. A sample characterization of total organic carbon, total        nitrogen, phosphorous, sulfide, sulfate, iron, methanogens, and        the like.    -   2. Addition of alkali solutions and/or surfactants to increase        availability of the materials to be treated.    -   3. Optimization of nutrients, add easy substrates for population        growth, add compounds to eliminate inhibitors (e.g., sulfide).    -   4. Engineering temperature control to maintain 30-40° C. and        anaerobic conditions of the ex-situ reactor (pit, aboveground        structures).

Embodiments of the present invention may include methods and systems forin-situ enhancement of biogenic methane production. This may be appliedto various hydrocarbon-bearing formations. In particular, an embodimentmay apply to oil shale formations (17) such as shown in FIGS. 17A-F. Itmay be desirable to locate an oil shale formation having perhaps anamendment-containing upper layer (18) and an oil shale layer (19). Inembodiments, an oil shale formation may include an overburden (25), anamendment-containing upper layer (18), an oil shale layer (19), andperhaps even an underburden (26). In other embodiments, it may bedesirable to locate an oil shale formation having perhaps at least onemicrobial population stimulation amendment. Depending on the oil shalesource, some may not have upper layers or even overlying materials overan oil shale formation. In embodiment, microbial population stimulationamendment(s) may include an indigenous microbial population stimulationamendment of which they may be located throughout an oil shaleformation. Fracturing of an oil shale formation or perhaps even of anamendment-containing upper layer of said oil shale formation may occursuch as with an oil shale formation fracture element or perhaps evenwith an upper layer fracture element (20). Fractures (27) may occurthroughout the oil shale formation as shown in FIG. 17B. A fracturingprocess may include drilling, breaking, an explosion, or the like of theupper layer as one skilled in the art could appreciate. A fractured oilshale layer or perhaps even a fractured upper layer may allow amendmentsthat were originally present in a formation or perhaps in a layer to beloosen from or even broken apart. These amendments may then be deliveredto at least one microbial population perhaps with a microbial populationstimulation amendment delivery element. In other embodiments, amendmentsmay then be carried from an upper layer to an oil shale layer perhapswith an upper layer amendment delivery element.

In embodiments, a microbial population stimulation amendment deliveryelement or perhaps even an upper layer amendment delivery element mayinclude liquid which can be injected through the fractures of an oilshale formation, as shown in FIG. 17C. A liquid injection element canprovide liquid (28) flowing throughout an oil shale formation and mayeven provide in other embodiment liquid flowing from an upper layer downto an oil shale layer as shown in FIG. 17D. Movement of at least onemicrobial population stimulation amendment (21) within a fractured oilshale formation can be understood in FIGS. 17E and 17F. Amendments (21)may spread throughout an oil shale layer. Embodiments may include awater injection element of which water may be injected through afractured amendment-containing upper layer of an oil shale formation. Inyet other embodiments, the present invention may provide a recycledwater injection element of which recycled water may be injected througha fractured amendment-containing upper layer. Each of the variousinjection embodiments may carry amendments within an oil shale formationor perhaps even from an upper layer to an oil shale layer.

The newly delivered amendment(s) may perhaps stimulate at least onemicrobial population located in an oil shale formation. In embodiments,at least one microbial population may include an indigenous microbialpopulation which may have pre-existed with an oil shale formation. Atleast one microbial population may even include at least one methanogenpopulation, in embodiments. As described above, stimulation of microbialpopulations perhaps from microbial population stimulation amendment(s)may then generate methane. It may then be desirable to collect theproduced methane perhaps even with a methane collection element asdiscussed herein.

A microbial population stimulation amendment may include but is notlimited to amendments such as sodium bicarbonate, sodium carbonate,hydrated sodium carbonate, nahcolite containing amendments, tronacontaining amendments, any combination thereof, and the like. Theseamendments may provide appropriate stimulation of microbial populationsin the oil shale layer to biogenically produce methane. This may providea system to which methane production can be efficiently enhanced.

A vast majority of oil shale deposited in southwestern Wyoming, GreenRiver, Wyoming, northwestern Colorado and eastern Utah may havenahcolite interbedded with the oil shale. Fracturing of this materialmay be easily done due to the relatively soft nature of the rock as oneskilled in the art can appreciate. Oil shales may tend to have lowstrength both in compression and in tension. The oil shale beds thatunderlie the trona beds may be small in volume compared to the massiveoil shale beds noted above. Trona may be more difficult to fracture dueto its inherent strength. It can test from 2501 to 7000 psi incompressive strength and could exhibit at least double the tensilestrength of oil shale. Accordingly, trona could be fractured anddissolved in a similar manner as could be done with massive oil shalebeds/deposits, or the like.

In yet other embodiments, it may be desirable to inject liquid andperhaps at least one additional amendment through a fracturedamendment-containing upper layer of an oil shale formation such as withan additional amendment injection element. An additional amendmentinjection element may include the addition of amendments through anupper layer and delivery of the newly added amendment(s) to an oil shalelayer. Additional amendments may include, but are not limited to,nitrogen, phosphorous, vitamins, organic carbon, biotin, folic acid,pyrodoxine hydrochloride, thiamine hydrochloride, riboflavin, nicotinicacid, DL-calcium panthenate, vitamin B12, p-aminobenzoic acid, liponicacid, any combination thereof, and the like. In other embodiments,additional amendments may include but are not limited to biowastes,lactate, milk, returned milk, nitrogen, phosphorous, vitamins, salts,micronutrients, surfactants, acids, bases, oxidants, acetic acid, sodiumhydroxide, percarbonate, peroxide, sodium carbonate, sodium bicarbonate,hydrated sodium carbonate, any combination thereof, and the like.

As discussed herein, the present invention may include, in embodiments,an ex situ bioreactor to produce methane. Ex-situ systems may providedegradation and perhaps even enhancement of methane production from coalseam, waste coal, oil shale, coal, coal derivatives, peat, lignite, oilformations, tar sands, and the like. Ex-situ systems may be used afterin-situ operations are completed in an attempt to extract all possibleresources from a particular formation. Ex-situ systems may include invarious embodiments: introduction of amendments such as substrates,nutrients, and the like; enhancement of organic matter released(physical, chemical, etc.); starvation and even selection of capablemethanogens; diminishing sulfate competition; boosting a population ofmethanogens, any combination of these and the like as discussed herein.As an example, extracted CBM water can be used as a medium and stored ina sealed container, ditch, pit, underground containment or above groundsystem, or the like. An ex-situ system may include any type ofnon-subterranean environment. In an embodiment, fine coal and perhapseven low value coal may be crushed and may be amended with additionalamendments (biowastes, lactate, returned milk etc), and even withessential nutrients. Nitrite and ferrous iron can be added perhaps whena sulfate concentration may be high in the CBM water. A system can beset up so that methane produced may be collected and stored. Aftercertain time of operation, a CBM water in the system may be injectedinto a site of interest to continue to generate CBM.

As an example, embodiments of the invention can be applied to apost-harvested site of altered oil shale, coal and the like. Theinvasive methods during the previous extraction activities such as oilshale retorting may create channels for a bioreaction as describedabove. A combination of enhancements may be applied to establish andenhance methane production from the residuals left in the site.

Operations such as oil shale retorting may leave residual hydrocarboncompounds in a post-harvested shale and water used during theoperations. Water might be of environmental concern due to an elevatedcontent of certain hydrocarbon compounds. The invention, in embodiments,can be applied to degrade hydrocarbon compounds in such water solely orperhaps even by mixing with other organic materials (e.g., agriculturewastes, oil shale structures and the like). The process may be carriedout either in-situ or ex-situ. Biogenic methane may be produced as aside product during the biodegradation of the otherwise contaminantmaterials.

Example 1

As an example, treatments were tested with oil shale in which resultsare shown in FIGS. 1 and 2. Treatment 1 includes nutrients. Treatment 2includes milk and nutrients. Treatment 3 includes inoculated substances,milk and nutrients. In FIG. 1, the control was left at 100% at both 7-12and 49-55 days and the percent increase was calculated relative to thecontrol values. In FIG. 2, the control was set at 7-12 days at 100% andthe percent increase was calculated relative to the control value at thefirst point.

Example 2

Microbes were established in 160 mL glass serum bottles with septa toprevent oxygen exposure. Duplicates were established for each treatment,including non-amended sterile controls. Microbes were established sothat 50 mL of headspace was remaining after setup for CH₄ production.Microbes were stored between 20-25° C. throughout the study. Amounts ofsubstrate and water used for microbe establishment are shown in Table 2.

TABLE 2 Carbon source and water amounts used for microbe establishment.Amount of Carbon Source, Carbon Source g Water, mL Oil Shale 75.0 63.0Coal 64.3 54.0 Lignite 61.9 520 Peat 75.0 63.0 Contaminated Soil 77.465.0

Data from baseline characterizations were used to calculate nutrientamendments in corresponding microbes. Analytical results indicated thatnitrogen (N) and phosphorus (P) were limiting for an optimal molar ratioof 100:30:3. Concentrations of N and P were increased using NH₄Cl andKH₂PO₄ respectively. Other additions included dump milk and bacterialinhibitors (2-BESA sodium salt, vancomycin.HCl and NaNO₂). Tables 3-7lists the treatments and amounts of treatments added to the microbes foreach carbon source.

TABLE 3 Nutrients and inhibitors added to oil shale microbes. Microbe IDCBM Water Groundwater 1 No additives No additives 2 0.0122 g 2-BESAsodium salt 0.0122 g 2-BESA sodium salt 3 0.0116 g Vancomycin•HCl 0.0116g Vancomycin•HCl 4 0.0240 g NaNO₂ 0.0240 g NaNO₂ 5 1.9515 g KH₂PO₄1.9494 g KH₂PO₄ 7.6688 g NH₄Cl 7.6601 g NH₄Cl 6 12.6 mL Milk 12.6 mLMilk 7 12.6 mL Milk 12.6 mL Milk 7.9638 g NH₄Cl 7.9551 g NH₄Cl 2.0266 gKH₂PO₄ 2.0245 g KH₂PO₄ 8 12.6 mL Milk 12.6 mL Milk 7.9638 g NH₄Cl 7.9551g NH₄Cl 2.0266 g KH₂PO₄ 2.0245 g KH₂PO₄ 0.0116 g Vancomycin•HCl 0.0116 gVancomycin•HCl 9 12.6 mL Milk 12.6 mL Milk 7.9638 g NH₄Cl 7.9551 g NH₄Cl2.0266 g KH₂PO₄ 2.0245 g KH₂PO₄ 0.0122 g 2-BESA sodium salt 0.0122 g2-BESA sodium salt 10 12.6 mL Milk 12.6 mL Milk 7.9638 g NH₄Cl 7.9551 gNH₄Cl 2.0266 g KH₂PO₄ 2.0245 g KH₂PO₄ 0.0240 g NaNO₂ 0.0240 g NaNO₂ 111.9515 g KH₂PO₄ 1.9494 g KH₂PO₄ 7.6688 g NH₄Cl 7.6601 g NH₄Cl 0.0240 gNaNO₂ 0.0240 g NaNO₂ 12 (Sterilized CBM Water) (Sterilized Groundwater)(Sterilized Oil Shale) (Sterilized Oil Shale) 13 (Sterilized Oil Shale)(Sterilized Oil Shale) 14 12.6 mL Milk 12.6 mL Milk 7.9638 g NH₄Cl7.9551 g NH₄Cl 2.0266 g KH₂PO₄ 2.0245 g KH₂PO₄ (Sterilized Oil Shale)(Sterilized Oil Shale)

TABLE 4 Nutrients and inhibitors added to coal microbes. Microbe ID CBMWATER WELL WATER 1 Nothing Nothing 2 0.0122 g 2-BESA 0.0122 g 2-BESA 30.0116 g vancomycin 0.0116 g vancomycin 4 0.0240 g NaNO₂ 0.0240 g NaNO₂5 0.0125 g NH₄Cl 0.0053 g NH₄Cl 0.0043 g KH₂PO₄ 0.0024 g KH₂PO₄ 6 12.6ml Milk 12.6 ml Milk 7 12.6 ml Milk 12.6 ml Milk 0.3075 g NH4Cl 0.3003 gNH4Cl 0.0794 g KH2PO4 0.0775 g KH2PO4 8 12.6 ml Milk 12.6 ml Milk 0.3075g NH₄Cl 0.3003 g NH₄Cl 0.0794 g KH₂PO₄ 0.0775 g KH₂PO₄ 0.0116 gvancomycin 0.0116 g vancomycin 9 12.6 ml Milk 12.6 ml Milk 0.3075 gNH₄Cl 0.3003 g NH₄Cl 0.0794 g KH₂PO₄ 0.0775 g KH₂PO₄ 0.0122 g 2-BESA0.0122 g 2-BESA 10 12.6 ml Milk 12.6 ml Milk 0.3075 g NH₄Cl 0.3003 gNH₄Cl 0.0794 g KH₂PO₄ 0.0775 g KH₂PO₄ 0.0240 g NaNO₂ 0.0240 g NaNO₂ 110.0125 g NH₄Cl 0.0053 g NH₄Cl 0.0043 g KH₂PO₄ 0.0024 g KH₂PO₄ 0.0240 gNaNO₂ 0.0240 g NaNO₂ 12 Sterile Solid Sterile Solid Sterile WaterSterile Water 13 Sterile Solid Sterile Solid Live Water Live Water 1412.6 ml Milk 12.6 ml Milk 0.3075 g NH₄Cl 0.3003 g NH₄Cl 0.0794 g KH₂PO₄0.0775 g KH₂PO₄ Sterile Solid Sterile Solid Live Water Live Water

TABLE 5 Nutrients and inhibitors added to lignite microbes. Microbe IDCBM WATER WELL WATER 1 Nothing Nothing 2 0.0122 g 2-BESA 0.0122 g 2-BESA3 0.0116 g vancomycin 0.0116 g vancomycin 4 0.0240 g NaNO₂ 0.0240 gNaNO₂ 5 0.0251 g NH₄Cl 0.0182 g NH₄Cl 0.0043 g KH₂PO₄ 0.0038 g KH₂PO₄ 612.6 ml Milk 12.6 ml Milk 7 12.6 ml Milk 12.6 ml Milk 0.3201 g NH4Cl0.3132 g NH4Cl 0.0794 g KH2PO4 0.0789 g KH2PO4 8 12.6 ml Milk 12.6 mlMilk 0.3201 g NH₄Cl 0.3132 g NH4Cl 0.0794 g KH₂PO₄ 0.0789 g KH₂PO₄0.0116 g vancomycin 0.0116 g vancomycin 9 12.6 ml Milk 12.6 ml Milk0.3201 g NH₄Cl 0.3132 g NH4Cl 0.0794 g KH₂PO₄ 0.0789 g KH₂PO₄ 0.0122 g2-BESA 0.0122 g 2-BESA 10 12.6 ml Milk 12.6 ml Milk 0.3201 g NH₄Cl0.3132 g NH4Cl 0.0794 g KH₂PO₄ 0.0789 g KH₂PO₄ 0.0240 g NaNO₂ 0.0240 gNaNO₂ 11 0.0251 g NH₄Cl 0.0182 g NH₄Cl 0.0043 g KH₂PO₄ 0.0038 g KH₂PO₄0.0240 g NaNO₂ 0.0240 g NaNO₂ 12 Sterile Solid Sterile Solid SterileWater Sterile Water 13 Sterile Solid Sterile Solid Live Water Live Water14 12.6 ml Milk 12.6 ml Milk 0.3201 g NH₄Cl 0.3132 g NH4Cl 0.0794 gKH₂PO₄ 0.0789 g KH₂PO₄ Sterile Solid Sterile Solid Live Water Live Water

TABLE 6 Nutrients and inhibitors added to peat microbes. Microbe ID CBMWATER WELL WATER 1 Nothing Nothing 2 0.0122 g 2-BESA 0.0122 g 2-BESA 30.0116 g vancomycin 0.0116 g vancomycin 4 0.0240 g NaNO₂ 0.0240 g NaNO₂5 0.0685 g NH₄Cl 0.0601 g NH₄Cl 0.0183 g KH₂PO₄ 0.0161 g KH₂PO₄ 6 12.6ml Milk 12.6 ml Milk 7 12.6 ml Milk 12.6 ml Milk 3.61 g NH4Cl 3.60 gNH4Cl 0.9191 g KH2PO4 0.9169 g KH2PO4 8 12.6 ml Milk 12.6 ml Milk 3.61 gNH4Cl 3.60 g NH4Cl 0.9191 g KH₂PO₄ 0.9169 g KH₂PO₄ 0.0116 g vancomycin0.0116 g vancomycin 9 12.6 ml Milk 12.6 ml Milk 3.61 g NH4Cl 3.60 gNH4Cl 0.9191 g KH₂PO₄ 0.9169 g KH₂PO₄ 0.0122 g 2-BESA 0.0122 g 2-BESA 1012.6 ml Milk 12.6 ml Milk 3.61 g NH4Cl 3.60 g NH4Cl 0.9191 g KH₂PO₄0.9169 g KH₂PO₄ 0.0240 g NaNO₂ 0.0240 g NaNO₂ 11 0.0685 g NH₄Cl 0.0601 gNH₄Cl 0.0183 g KH₂PO₄ 0.0161 g KH₂PO₄ 0.0240 g NaNO₂ 0.0240 g NaNO₂ 12Sterile Solid Sterile Solid Sterile Water Sterile Water 13 Sterile SolidSterile Solid Live Water Live Water 14 12.6 ml Milk 12.6 ml Milk 3.61 gNH4Cl 3.60 g NH4Cl 0.9191 g KH₂PO₄ 0.9169 g KH₂PO₄ Sterile Solid SterileSolid Live Water Live Water

TABLE 7 Nutrients and inhibitors added to contaminated soil microbes.Microbe ID CBM WATER WELL WATER 1 Nothing Nothing 2 0.0122 g 2-BESA0.0122 g 2-BESA 3 0.0116 g vancomycin 0.0116 g vancomycin 4 0.0240 gNaNO₂ 0.0240 g NaNO₂ 5 12.92 g NH₄Cl 12.92 g NH₄Cl 3.29 g KH₂PO₄ 3.29 gKH₂PO₄ 6 13 ml Milk 13 ml Milk 7 13 ml Milk 13 ml Milk 16.58 g NH4Cl16.57 g NH4Cl 4.22 g KH2PO4 4.22 g KH2PO4 8 13 ml Milk 13 ml Milk 16.58g NH₄Cl 16.57 g NH₄Cl 4.22 g KH₂PO₄ 4.22 g KH₂PO₄ 0.0116 g vancomycin0.0116 g vancomycin 9 13 ml Milk 13 ml Milk 16.58 g NH₄Cl 16.57 g NH₄Cl4.22 g KH₂PO₄ 4.22 g KH₂PO₄ 0.0122 g 2-BESA 0.0122 g 2-BESA 10 13 mlMilk 13 ml Milk 16.58 g NH₄Cl 16.57 g NH₄Cl 4.22 g KH₂PO₄ 4.22 g KH₂PO₄0.0240 g NaNO₂ 0.0240 g NaNO₂ 11 12.92 g NH₄Cl 12.92 g NH₄Cl 3.29 gKH₂PO₄ 3.29 g KH₂PO₄ 0.0240 g NaNO₂ 0.0240 g NaNO₂ 12 Sterile SolidSterile Solid Sterile Water Sterile Water 13 Sterile Solid Sterile SolidLive Water Live Water 14 13 ml Milk 13 ml Milk 16.58 g NH₄Cl 16.57 gNH₄Cl 4.22 g KH₂PO₄ 4.22 g KH₂PO₄ Sterile Solid Sterile Solid Live WaterLive Water

Example 3

A separate set of microbes were established to increase thebioavailability of organics. This was done by pre-treating the crushedoil shale with 1 M sodium hydroxide (NaOH). 1 M NaOH solution was addedto the oil shale until a pH of 13 was attained and the mixture wasallowed to react for 24 hours at room temperature and under nitrogenatmosphere. The pH was lowered to 9.8 by adding HCl before the additionof treatments and increasing the liquid volume to 63 mL. As before, themicrobes were created anaerobically in the same manner as outlinedbefore. The information Table 8 lists the microbes created along withcorresponding amendments.

TABLE 8 Nutrients and inhibitors added to groundwater (63 mL) mixed withpre-treated oil shale (75 g) with NaOH. Microbe ID Groundwater 1 NoAdditives 2 1.9494 g KH₂PO₄ 7.6601 g NH₄Cl 3 12.6 ml milk 4 2.0245 gKH₂PO₄ 7.9551 g NH4Cl 12.6 ml milk 5 (Sterilized Groundwater)(Sterilized Oil Shale) 6 (Sterilized Oil Shale) No Amendments 7(Sterilized Oil Shale) 2.045 g KH₂PO₄ 7.9551 g NH₄Cl 12.6 ml milk

The results may show that nutrient-amended, especially nutrient plussubstrate amended, treatments produced the highest amount of methanefrom microbes containing coal CBM co-produced water, as shown in FIG. 3.Nutrients may substantially increase the rate of methane productionafter 60 days from microbes containing coal and groundwater, as shown inFIG. 4. The cumulative amount of methane produced from those treatmentssurpassed the live control after 100 days. Nutrient amendments may havehad little effect on methane production in microbes containing lignite,as shown in FIGS. 5 and 6. The addition of nutrients to thediesel-contaminated soil may have had an inhibitory effect since themethane production in the controls was occurring at a greater rate, asshown in FIGS. 7 and 8. Aerobic bacteria may be dominant in numbers inthe soil, which could consume the remaining oxygen in the system andproduce carbon dioxide from the oxidation of the hydrocarbons. Otherpopulations of anaerobic bacteria, such as facultative and strictlydenitrifying bacteria, may exist in higher numbers in the soil, whichmay breakdown hydrocarbons to simpler molecules and carbon dioxide;however, methanogen population were not detected in this soil.Therefore, only the groundwater and CBM co-produced water may havesupplied a methanogen population. An incubation period of greater than60 days may be necessary for methanogenic conditions to dominate. FIG. 9shows the cumulative methane production from microbes with peat and CBMco-produced water. Nutrient additions to microbes containing peat didhave a positive effect on methane production as shown in FIG. 10.

The results from the groundwater-oil shale microbes may show that whilemethane production rate stabilizes, a higher concentration of carbondioxide may be produced, as shown in FIGS. 11, 12 a and 12 b. Thisresult may also be occurring with the groundwater-oil shale microbescontaining the pre-treated oil shale. One possible problem was that thetemperature of the room (˜20° C.) was not optimal for methanogenesis,and a temperature of ˜30° C. could be more adequate since this is theestimated temperature of oil shale at its source depth. The microbeswere split into two groups: incubated at 30° C. and incubated at roomtemperature.

In general, incubation at 30° C. may increase methane production rateand may increase the rate of carbon dioxide, see FIGS. 13 a, 13 b and 14a. Pre-treatment with nutrients may have a 30 fold increase in methaneproduction rate, while the rate of carbon dioxide may decrease. This maysubstantially increase the methane to carbon dioxide volume ratio tomore than 22, see FIG. 14 b. This may suggest that pre-treatment andenhancement injections into oil shale reservoirs can substantiallyincrease the rate of methane production and may reduce an amount ofcarbon dioxide.

Example 4

Oil shale used in the previous tests was cored to a diameter of 10.16cm. These cores were fractured using a Soiltest Mechanical SoilCompactor Model CN-4235 (Lake Bluff, Ill.). The soil compactor drops a4.54 kg shaft, 0.45 m at 2.12 m/s. Reactors were separated and groupedby fracture and treatment designation (Table 9). The treatments used inthis test were chosen from those that performed the best in previoustrials. Oil shale permeability and hydraulic conductivity were measuredby flexible-wall parameters and were determined to be 3.09×10⁻⁹ cm² and3.41×10⁻⁷ cm/s, respectively. Microbial activity is evident from thehigh production of carbon dioxide; however relatively small amount ofmethane is being produced, as shown in FIGS. 15 a and 15 b. Similar tothe microbe studies described above, the reactors were incubated at roomtemperature (˜20° C.). Considering the effects that incubating at 30° C.had onto those microbes, incubating the reactors at the same temperaturemay increase methane production.

TABLE 9 Fracture and treatment designations for the scaled-up reactorsFracture ID (Group) Designation Treatment 1  0 Hits 2 15 Hits 3 30 Hits4 45 Hits 5 60 Hits A No Amendments B NaOH Pre-treatment C NaOHPre-treatment + Nutrients D NaOH Pre-treatment + nutrients + milk

Pre-treatment and addition of nutrients may substantially increase therate of methane production perhaps even when exposed to temperatureswhere the oil-shale and water were collected (˜30° C. in this case). Thepre-treatment may extract the carbon source (hydrocarbons in this case)from the solid and makes it more bioavailable for microbial degradationand transformation. The adjustment of temperature to the level foundwhere the shale was collected is optimal for microbial (methanogenic)activity. The microbe studies with coal, lignite, peat, anddiesel-contaminated soil did not involve pre-treatments, which may havelimited the availability of the carbon. Also, the microbes wereincubated at room temperature (˜20° C.), which may not have been theoptimal (natural) temperature for methanogenic activity.

As can be easily understood from the foregoing, the basic concepts ofthe present invention may be embodied in a variety of ways. It involvesboth methane production techniques as well as devices to accomplish theappropriate methane system. In this application, the methane productiontechniques are disclosed as part of the results shown to be achieved bythe various devices described and as steps which are inherent toutilization. They are simply the natural result of utilizing the devicesas intended and described. In addition, while some devices aredisclosed, it should be understood that these not only accomplishcertain methods but also can be varied in a number of ways. Importantly,as to all of the foregoing, all of these facets should be understood tobe encompassed by this disclosure.

The discussion included in this application is intended to serve as abasic description. The reader should be aware that the specificdiscussion may not explicitly describe all embodiments possible; manyalternatives are implicit. It also may not fully explain the genericnature of the invention and may not explicitly show how each feature orelement can actually be representative of a broader function or of agreat variety of alternative or equivalent elements. Again, these areimplicitly included in this disclosure. Where the invention is describedin device-oriented terminology, each element of the device implicitlyperforms a function. Apparatus claims may not only be included for thedevice described, but also method or process claims may be included toaddress the functions the invention and each element performs. Neitherthe description nor the terminology is intended to limit the scope ofthe claims included herein or in any subsequent patent application.

It should also be understood that a variety of changes may be madewithout departing from the essence of the invention. Such changes arealso implicitly included in the description. They still fall within thescope of this invention. A broad disclosure encompassing both theexplicit embodiment(s) shown, the great variety of implicit alternativeembodiments, and the broad methods or processes and the like areencompassed by this disclosure and may be relied upon when drafting theclaims for any subsequent patent application. It should be understoodthat such language changes and broader or more detailed claiming may beaccomplished at a later date (such as by any required deadline) or inthe event the applicant subsequently seeks a patent filing based on thisfiling. With this understanding, the reader should be aware that thisdisclosure is to be understood to support any subsequently filed patentapplication that may seek examination of as broad a base of claims asdeemed within the applicant's right and may be designed to yield apatent covering numerous aspects of the invention both independently andas an overall system.

Further, each of the various elements of the invention and claims mayalso be achieved in a variety of manners. Additionally, when used orimplied, an element is to be understood as encompassing individual aswell as plural structures that may or may not be physically connected.This disclosure should be understood to encompass each such variation,be it a variation of an embodiment of any apparatus embodiment, a methodor process embodiment, or even merely a variation of any element ofthese. Particularly, it should be understood that as the disclosurerelates to elements of the invention, the words for each element may beexpressed by equivalent apparatus terms or method terms—even if only thefunction or result is the same. Such equivalent, broader, or even moregeneric terms should be considered to be encompassed in the descriptionof each element or action. Such terms can be substituted where desiredto make explicit the implicitly broad coverage to which this inventionis entitled. As but one example, it should be understood that allactions may be expressed as a means for taking that action or as anelement which causes that action. Similarly, each physical elementdisclosed should be understood to encompass a disclosure of the actionwhich that physical element facilitates. Regarding this last aspect, asbut one example, the disclosure of an “injector” should be understood toencompass disclosure of the act of “injecting”—whether explicitlydiscussed or not—and, conversely, were there effectively disclosure ofthe act of “injecting”, such a disclosure should be understood toencompass disclosure of an “injector” and even a “means for injecting.”Such changes and alternative terms are to be understood to be explicitlyincluded in the description.

Any patents, publications, or other references mentioned in thisapplication for patent are hereby incorporated by reference. Anyapplications or patents claimed under priority in this or any subsequentapplications are also hereby incorporated by reference. In addition, asto each term used it should be understood that unless its utilization inthis application is inconsistent with a broadly supportinginterpretation, common dictionary definitions should be understood asincorporated for each term and all definitions, alternative terms, andsynonyms such as contained in the Random House Webster's UnabridgedDictionary, second edition are hereby incorporated by reference.Finally, all references listed in the table below or other informationstatement filed with the application are hereby appended and herebyincorporated by reference, however, as to each of the above, to theextent that such information or statements incorporated by referencemight be considered inconsistent with the patenting of this/theseinvention(s) such statements are expressly not to be considered as madeby the applicant(s).

I. U.S. PATENT DOCUMENTS

PATENTEE DOCUMENT NO. & PUB'N DATE OR APPLICANT KIND CODE (if known)mm-dd-yyyy NAME 2004/0033557 A1 02-19-2004 Scott et al. 2004/0200618 A110-14-2004 Piekenbrock 2005/0061001 A1 03-24-2005 Maston 2005/0082058 A104-21-2005 Bustin et al. 3,640,846 02-8-1972 Johnson 3,826,30807-30-1974 Compere-Whitney 4,151,068 04-24-1979 McCollum et al.4,358,537 11-9-1982 Chynoweth 4,826,769 05-2-1989 Menger 4,845,03407-04-1989 Menger et al. 4,883,753 11-28-1989 Belaich et al. 5,340,3768-23-1994 Cunningham 5,350,684 09-27-1994 Nakatsugawa et al. 5,424,19506-13-1995 Volkwein 5,494,108 02-27-1996 Palmer et al. 5,566,75610-22-1996 Chaback et al. 5,670,345 09-23-1997 Srivastava et al.5,919,696 07-06-1999 Ikeda et al. 6,090,593 07-18-2000 Fleming et al.6,210,955 B1 4-3-2001 Hayes 6,543,535 B2 04-08-2003 Converse et al.6,571,874 B1 06-03-2003 Lovenich et al. 6,571,874 B1 3-16-2000 Lovenichet al.

II. FOREIGN PATENT DOCUMENTS

Foreign Patent Document Country Code, Number, Kind Code PUB'N DATEPATENTEE OR APPLICANT (if known) mm-dd-yyyy NAME WO94/25730 11-10-1994Exxon Chemical Patents Inc. WO2004/003506 A2 01-08-2004 Well-Dog, Inc.WO79/00201 04-19-1979 Vyrmetoder et al. WO01/68904 A1 9-20-2001Exxonmobil Upstream Research Co.

Thus, the applicant(s) should be understood to have support to claim andmake a statement of invention to at least: i) each of the methaneproduction devices as herein disclosed and described, ii) the relatedmethods disclosed and described, iii) similar, equivalent, and evenimplicit variations of each of these devices and methods, iv) thosealternative designs which accomplish each of the functions shown as aredisclosed and described, v) those alternative designs and methods whichaccomplish each of the functions shown as are implicit to accomplishthat which is disclosed and described, vi) each feature, component, andstep shown as separate and independent inventions, vii) the applicationsenhanced by the various systems or components disclosed, viii) theresulting products produced by such systems or components, ix) eachsystem, method, and element shown or described as now applied to anyspecific field or devices mentioned, x) methods and apparatusessubstantially as described hereinbefore and with reference to any of theaccompanying examples, xi) the various combinations and permutations ofeach of the elements disclosed, and xii) each potentially dependentclaim or concept as a dependency on each and every one of theindependent claims or concepts presented.

With regard to claims whether now or later presented for examination, itshould be understood that for practical reasons and so as to avoid greatexpansion of the examination burden, the applicant may at any timepresent only initial claims or perhaps only initial claims with onlyinitial dependencies. Support should be understood to exist to thedegree required under new matter laws—including but not limited toEuropean Patent Convention Article 123(2) and United States Patent Law35 USC 132 or other such laws—to permit the addition of any of thevarious dependencies or other elements presented under one independentclaim or concept as dependencies or elements under any other independentclaim or concept. In drafting any claims at any time whether in thisapplication or in any subsequent application, it should also beunderstood that the applicant has intended to capture as full and broada scope of coverage as legally available. To the extent thatinsubstantial substitutes are made, to the extent that the applicant didnot in fact draft any claim so as to literally encompass any particularembodiment, and to the extent otherwise applicable, the applicant shouldnot be understood to have in any way intended to or actuallyrelinquished such coverage as the applicant simply may not have beenable to anticipate all eventualities; one skilled in the art, should notbe reasonably expected to have drafted a claim that would have literallyencompassed such alternative embodiments.

Further, if or when used, the use of the transitional phrase“comprising” is used to maintain the “open-end” claims herein, accordingto traditional claim interpretation. Thus, unless the context requiresotherwise, it should be understood that the term “comprise” orvariations such as “comprises” or “comprising”, are intended to implythe inclusion of a stated element or step or group of elements or stepsbut not the exclusion of any other element or step or group of elementsor steps. Such terms should be interpreted in their most expansive formso as to afford the applicant the broadest coverage legally permissible.

Finally, any claims set forth at any time are hereby incorporated byreference as part of this description of the invention, and theapplicant expressly reserves the right to use all of or a portion ofsuch incorporated content of such claims as additional description tosupport any of or all of the claims or any element or component thereof,and the applicant further expressly reserves the right to move anyportion of or all of the incorporated content of such claims or anyelement or component thereof from the description into the claims orvice-versa as necessary to define the matter for which protection issought by this application or by any subsequent continuation, division,or continuation-in-part application thereof, or to obtain any benefitof, reduction in fees pursuant to, or to comply with the patent laws,rules, or regulations of any country or treaty, and such contentincorporated by reference shall survive during the entire pendency ofthis application including any subsequent continuation, division, orcontinuation-in-part application thereof or any reissue or extensionthereon.

1. A method for enhancement of biogenic methane production comprisingthe steps of: providing a hydrocarbon-bearing formation having at leasttwo microbial populations; introducing at least one indiscriminatemicrobial population stimulation amendment to said hydrocarbon-bearingformation having said at least two microbial populations; microbiallyconsuming said at least one indiscriminate microbial populationstimulation amendment by said at least two microbial populations;blanket boosting said at least two microbial populations of saidhydrocarbon-bearing formation from consumption of said at least oneindiscriminate microbial population stimulation amendment; microbiallydepleting said at least one indiscriminate microbial populationstimulation amendment; starving at least one of said at least twoboosted microbial populations; selectively reducing said starved atleast one of said at least two boosted microbial populations;selectively sustaining said at least one boosted microbial population;generating methane from said at least one boosted microbial population;and collecting said methane.
 2. A method for enhancement of biogenicmethane production according to claim 1 wherein said at least oneindiscriminate microbial population stimulation amendment is selectedfrom a group consisting of corn syrup, emulsified oil, lactate, freshmilk, spoiled milk, and any combination thereof.
 3. A method forenhancement of biogenic methane production according to claim 1 andfurther comprising the step of introducing at least one additionalmicrobial population stimulation amendment.
 4. A method for enhancementof biogenic methane production according to claim 3 wherein said atleast one additional microbial population stimulation amendment isselected from a group consisting of nitrogen, phosphorous, vitamins,organic carbon, biotin, folic acid, pyrodoxine hydrochloride, thiaminehydrochloride, riboflavin, nicotinic acid, DL-calcium panthenate,vitamin B12, p-aminobenzoic acid, lipoic acid, and any combinationthereof.
 5. A method for enhancement of biogenic methane productionaccording to claim 3 wherein said at least one additional microbialpopulation stimulation amendment is selected from a group consisting ofbiowastes, lactate, milk, returned milk, nitrogen, phosphorous,vitamins, salts, micronutrients, surfactants, acids, bases, oxidants,acetic acid, sodium hydroxide, percarbonate, peroxide, sodium carbonate,sodium bicarbonate, hydrated sodium carbonate, and any combinationthereof.
 6. A method for enhancement of biogenic methane productionaccording to claim 1 wherein said step of introducing at least oneindiscriminate microbial population stimulation amendment to saidhydrocarbon-bearing formation having said at least two microbialpopulations comprises the step of injecting recycled water carrying saidat least one indiscriminate microbial population stimulation amendmentinto said hydrocarbon-bearing formation.
 7. A method for enhancement ofbiogenic methane production according to claim 6 wherein said recycledwater comprises produced water.
 8. A method for enhancement of biogenicmethane production according to claim 6 wherein said recycled watercomprises groundwater.
 9. A method for enhancement of biogenic methaneproduction according to claim 6 wherein said recycled water compriseswater from coal bed methane production.
 10. A method for enhancement ofbiogenic methane production according to claim 1 wherein said step ofstarving at least one of said at least two boosted microbial populationscomprises the step of discontinuing said introduction of said at leastone indiscriminate microbial population stimulation amendment to saidhydrocarbon-bearing formation.
 11. A method for enhancement of biogenicmethane production according to claim 1 and further comprising the stepof introducing a sulfate reduction competition shield amendment intosaid hydrocarbon-bearing formation.
 12. A method for enhancement ofbiogenic methane production according to claim 11 wherein said sulfatereduction competition shield amendment is selected from a groupconsisting of nitrite, ferrous iron, and a combination of the two.
 13. Amethod for enhancement of biogenic methane production according to claim1 wherein said hydrocarbon-bearing formation is selected from a groupconsisting of oil shale, coal, coal seam, waste coal, coal derivatives,lignite, peat, oil formations, tar sands, petroleum sludge, drillcuttings, and hydrocarbon-contaminated soil.
 14. A method forenhancement of biogenic methane production according to claim 1 whereinsaid at least two microbial populations comprises an indigenousmicrobial population.
 15. A method for enhancement of biogenic methaneproduction according to claim 1 wherein said step of selectivelysustaining said at least one boosted microbial population comprises thestep of stimulating said at least one boosted microbial population. 16.A method for enhancement of biogenic methane production according toclaim 1 wherein said at least two microbial populations comprises atleast one methanogen population.
 17. A method for enhancement ofbiogenic methane production according to claim 1 wherein said step ofgenerating methane from said at least one boosted microbial populationcomprises the step of microbially converting hydrocarbons to methane.18. A method for enhancement of biogenic methane production according toclaim 1 wherein said hydrocarbon-bearing formation is located in anin-situ methane production environment.
 19. A method for enhancement ofbiogenic methane production according to claim 1 wherein saidhydrocarbon-bearing formation is located in an ex-situ methaneproduction environment.
 20. A method of in-situ enhancing biogenicmethane production comprising the steps of: locating an oil shaleformation having at least one microbial population stimulationamendment; fracturing said oil shale formation; delivering said at leastone microbial population stimulation amendment to at least one microbialpopulation; stimulating said at least one microbial population in saidoil shale formation with said at least one microbial populationstimulation amendment; generating methane from said at least onestimulated microbial population; collecting said methane; introducing atleast one indiscriminate microbial population stimulation amendment tosaid oil shale formation having at least two microbial populations;microbially consuming said at least one indiscriminate microbialpopulation stimulation amendment by said at least two microbialpopulations; blanket boosting said at least two microbial populations ofsaid oil shale formation from consumption of said at least oneindiscriminate microbial population stimulation amendment; microbiallydepleting said at least one indiscriminate microbial populationstimulation amendment; starving at least one of said at least twoboosted microbial population; selectively reducing said starved at leastone of said at least two boosted microbial populations; and selectivelysustaining said at least one boosted microbial population.
 21. A methodof in-situ enhancing biogenic methane production according to claim 20wherein said at least one microbial population stimulation amendment isselected from a group consisting of sodium bicarbonate, sodiumcarbonate, hydrated sodium carbonate, nahcolite containing amendments,trona containing amendments, and any combination thereof.
 22. A methodof in-situ enhancing biogenic methane production according to claim 20and further comprising the step of injecting liquid through saidfractured oil shale formation.
 23. A method of in-situ enhancingbiogenic methane production according to claim 22 wherein said step ofinjecting liquid through said fractured oil shale formation comprisesthe step of injecting liquid and at least one additional amendmentthrough said oil shale formation.
 24. A method of in-situ enhancingbiogenic methane production according to claim 23 wherein saidadditional amendment is selected from a group consisting of nitrogen,phosphorous, vitamins, organic carbon, biotin, folic acid, pyrodoxinehydrochloride, thiamine hydrochloride, riboflavin, nicotinic acid,DL-calcium panthenate, vitamin B12, p-aminobenzoic acid, liponic acid,and any combination thereof.
 25. A method of in-situ enhancing biogenicmethane production according to claim 23 wherein said additionalamendment is selected from a group consisting of biowastes, lactate,milk, returned milk, nitrogen, phosphorous, vitamins, salts,micronutrients, surfactants, acids, bases, oxidants, acetic acid, sodiumhydroxide, percarbonate, peroxide, sodium carbonate, sodium bicarbonate,hydrated sodium carbonate, and any combination thereof.
 26. A method ofin-situ enhancing biogenic methane production according to claim 23wherein said additional amendment comprises a sulfate reductioncompetition shield amendment.
 27. A method of in-situ enhancing biogenicmethane production according to claim 26 wherein said sulfate reductioncompetition shield amendment is selected from a group consisting ofnitrite, ferrous iron, and a combination of the two.
 28. A method ofin-situ enhancing biogenic methane production according to claim 20wherein said step of injecting liquid through said fractured oil shaleformation comprises the step of injecting water through said fracturedoil shale formation.
 29. A method of in-situ enhancing biogenic methaneproduction according to claim 28 wherein said step of injecting waterthrough said fractured oil shale formation comprises the step ofinjecting recycled water through said fractured oil shale formation. 30.A method of in-situ enhancing biogenic methane production according toclaim 29 wherein said recycled water comprises produced water.
 31. Amethod of in-situ enhancing biogenic methane production according toclaim 29 wherein said recycled water comprises groundwater.
 32. A methodof in-situ enhancing biogenic methane production according to claim 29wherein said recycled water comprises water from coal bed methaneproduction.
 33. A method of in-situ enhancing biogenic methaneproduction according to claim 20 wherein said at least one microbialpopulation comprises an indigenous microbial population.
 34. A method ofin-situ enhancing biogenic methane production according to claim 20wherein said microbial population stimulation amendment comprises anindigenous microbial population stimulation amendment.
 35. A method ofin-situ enhancing biogenic methane production according to claim 20wherein said step of stimulating said at least one microbial populationin said oil shale formation with said at least one microbial populationstimulation amendment comprises the steps of: increasing organic matterconcentrations within said oil shale formation; and feeding said atleast one microbial population.
 36. A method of in-situ enhancingbiogenic methane production according to claim 20 wherein said step ofstimulating said at least one microbial population in said oil shaleformation with said at least one microbial population stimulationamendment comprises the step creating a series of metabolic interactionsamong microbial populations with said at least one microbial populationstimulation amendment.
 37. A method of in-situ enhancing biogenicmethane production according to claim 20 wherein said at least onemicrobial population comprises at least one methanogen population.
 38. Amethod of in-situ enhancing biogenic methane production according toclaim 20 wherein said step of generating methane from said at least onestimulated microbial population comprises the step of microbiallyconverting hydrocarbons to methane.
 39. A method of in-situ enhancingbiogenic methane production according to claim 20 wherein said at leastone indiscriminate microbial population stimulation amendment isselected from a group consisting of corn syrup, emulsified oil, lactate,fresh milk, spoiled milk, and any combination thereof.
 40. A method ofin-situ enhancing biogenic methane production according to claim 20wherein said oil shale formation comprises an amendment containing upperlayer and an oil shale layer.
 41. A method of in-situ enhancing biogenicmethane production according to claim 40 wherein said step of fracturingsaid oil shale formation comprises the step of fracturing saidamendment-containing upper layer of said oil shale formation.
 42. Amethod of in-situ enhancing biogenic methane production according toclaim 41 and further comprising the steps of: injecting liquid throughsaid fractured amendment-containing upper layer of said oil shaleformation; and delivering at least one amendment from said fracturedupper layer to said oil shale layer with said liquid injection.
 43. Abiogenic methane production system comprising: a hydrocarbon-bearingformation environment initially having at least two microbialpopulations; at least one indiscriminate microbial populationstimulation amendment delivered to said hydrocarbon-bearing formationenvironment; at least one starved microbial population of said at leasttwo microbial populations; at least one sustained boosted microbialpopulation of said at least two microbial population; biogenicallygenerated methane derived from said at least one sustained boostedmicrobial population; and a methane collection element.
 44. A biogenicmethane production system according to claim 43 wherein saidindiscriminate microbial population stimulation amendment is selectedfrom a group consisting of corn syrup, emulsified oil, lactate, freshmilk, spoiled milk, and any combination thereof.
 45. A biogenic methaneproduction system according to claim 43 and further comprising at leastone introduced additional microbial population stimulation amendment.46. A biogenic methane production system according to claim 45 whereinsaid introduced additional microbial population stimulation amendment isselected from a group consisting of nitrogen, phosphorous, vitamins,organic carbon, biotin, folic acid, pyrodoxine hydrochloride, thiaminehydrochloride, riboflavin, nicotinic acid, DL-calcium panthenate,vitamin B12, p-aminobenzoic acid, liponic acid, and any combinationthereof.
 47. A biogenic methane production system according to claim 45wherein said introduced additional microbial population stimulationamendment is selected from a group consisting of biowastes, lactate,milk, returned milk, nitrogen, phosphorous, vitamins, salts,micronutrients, surfactants, acids, bases, oxidants, acetic acid, sodiumhydroxide, percarbonate, peroxide, sodium carbonate, sodium bicarbonate,hydrated sodium carbonate, and any combination thereof.
 48. A biogenicmethane production system according to claim 43 wherein saidindiscriminate microbial population stimulation amendment delivered tosaid hydrocarbon-bearing formation environment comprises saidindiscriminate microbial population stimulation amendment injected intosaid hydrocarbon-bearing formation environment in recycled water.
 49. Abiogenic methane production system according to claim 48 wherein saidrecycled water comprises produced water.
 50. A biogenic methaneproduction system according to claim 48 wherein said recycled watercomprises groundwater.
 51. A biogenic methane production systemaccording to claim 48 wherein said recycled water comprises water fromcoal bed methane production.
 52. A biogenic methane production systemaccording to claim 43 and further comprising a sulfate reductioncompetition shield amendment delivered to said hydrocarbon-bearingformation environment.
 53. A biogenic methane production systemaccording to claim 52 wherein said sulfate reduction competition shieldamendment is selected from a group consisting of nitrite, ferrous iron,and a combination of the two.
 54. A biogenic methane production systemaccording to claim 43 wherein said hydrocarbon-bearing formation isselected from a group consisting of oil shale, coal, coal seam, wastecoal, coal derivatives, lignite, peat, oil formations, tar sands,petroleum sludge, drill cuttings, and hydrocarbon-contaminated soil. 55.A biogenic methane production system according to claim 43 wherein saidat least two microbial population comprises an indigenous microbialpopulation.
 56. A biogenic methane production system according to claim43 wherein said at least two microbial populations comprises at leastone methanogen population.
 57. A biogenic methane production systemaccording to claim 43 wherein said biogenically generated methanecomprises methane produced from microbial conversion of hydrocarbons.58. A biogenic methane production system according to claim 43 whereinsaid hydrocarbon-bearing formation environment comprises an in-situhydrocarbon-bearing formation environment.
 59. A biogenic methaneproduction system according to claim 43 wherein said hydrocarbon-bearingformation environment comprises an ex-situ hydrocarbon-bearing formationenvironment.